CN103764372B - Double orientation polyethylene film - Google Patents

Double orientation polyethylene film Download PDF

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Publication number
CN103764372B
CN103764372B CN201180073064.9A CN201180073064A CN103764372B CN 103764372 B CN103764372 B CN 103764372B CN 201180073064 A CN201180073064 A CN 201180073064A CN 103764372 B CN103764372 B CN 103764372B
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China
Prior art keywords
film
vistanex
horizontal
orientation
linear low
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CN103764372A (en
Inventor
云小兵
丛蓉娟
J.潘
P.T.卡杰拉
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0625—LLDPE, i.e. linear low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/24992—Density or compression of components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses the method forming Biaxially oriented film.The method includes first selecting vistanex, wherein said vistanex includes that linear low density polyethylene resin, described linear low density polyethylene resin are characterized by the linear low density polyethylene resin eluted out in the temperature more than 97.0 DEG C of 9 35wt% of gross weight from CEF.

Description

Double orientation polyethylene film
Technical field
The present invention relates to double orientation polyethylene film, the preparation method of double orientation polyethylene film and polyethylene double orientation film for The purposes of flexible packaging.
Background technology and summary of the invention
Polyethylene film is widely used in flexible packaging (such as heavy haul transport packaging bag, durable bags, detergent bags, pouch etc.) In.Must provide for multiple character to meet packaging bag demand in terms of globality and captivation.These character include: 1) excellent Optical property, such as high gloss, the high grade of transparency and low haze；2) enough tamper resistances, such as high tensile, height are anti- Puncture and impact resistance；3) good sealed nature, the lowest sealing initiation temperature, wide sealed window, high sealing intensity and High heat-blocking.
Conventional blow or curtain coating polyethylene film are widely used in flexible packaging as independent packaging or laminate film.Along with city Field tends to sustainability, and the thickness of flexible packaging continues to reduce.Accordingly, it would be desirable to higher film hardness and the combination of toughness.For (or " PE ") film, 2% secant modulus is preferably from about 150-250MPa for conventional blown or curtain coating polyethylene.By introduce Midst density and High density PE, it is possible to increase hardness, but it will infringement toughness and film transparency.
Double orientation is that a kind of common manufacture method is to improve film hardness and toughness.The transparency of film, hardness and toughness are logical Cross orientation can be greatly improved.But, have also obtained shrinkage factor character by orientation.For the most soft packaging, residual shrinkage Rate is not applicable character, because the sealing caused in downstream lamination or printing process is tilted by higher residual shrinkage rate (winkles), dimensional instability or other problems.Existing most of polyethylene orientation technology (the most double bubbling method) sets Meter, to prepare shrink film, is not the basement membrane of dimensionally stable, such as the laminate film of flexible package.
U.S. Patent number 4,354,997 He4,463,153Disclose by biaxial stretch-formed (the lowest close by ethene polymers Degree polyethylene, linear low density polyethylene or ethylene are as key component and the copolymer of α-ethylenically unsaturated monomers) prepare not The tubular membrane of drawn prepares the method for biaxial orientation blow-molding polyethylene film.This unstretched pipe is made by internal air pressure Formula film is expanded on horizontal and vertical and extends simultaneously under specific temperature curve under given conditions.
European patent application 0240705 relates to heat-shrinkable, the biaxial stretch-formed tubular type of the mixture of (A) and (B) and blows Plastic film, (A) be 90-50wt% at 25 DEG C, there is 0.90-0.93g/cm3Density linear ethylene/alpha olefin copolymer and (B) be 10-50wt% at 25 DEG C, there is 0.87-0.91g/cm3And at least 0.014g/cm lower than the density of copolymer (A)3Close The ethene polymers of degree.This unstretched tubular membrane is made to expand and stretching by the air pressure in pipe, and simultaneously laterally With upper biaxial orientation.
British patent specification 866,820 relates to by high pressure or low-pressure polyethylene, polypropylene or ethylene/propene copolymer system Standby film.Ionize first passing around high energy by the polymeric material of uniaxially or biaxially stretch orientation in its preparation process Irradiation.Then this material heated and be oriented either uniaxially or biaxially, finally cooling down.Use tubular membrane as first time biaxial orientation Parent material.Due to irradiation, the high temperature tensile strength of this film is improved.Biaxial orientation after irradiation be by with air or Other gases or with liquid formed bubble make this film expansion and carry out.According to this bubbler techniques, prepare horizontal and vertical same Time orientation blown film.
U.S. Patent number 4,680,207 relate to biaxial orientation linear low density polyethylene film, and it is laterally little to arrive more than 1 Draw ratio in 3 stretches, and longitudinally with less than 6 but more than horizontal draw ratio stretching.This film is following preparation: by non-must The melted linear low density polyethylene extrusion of strategic point and low-density non-linear polyethylene mixed with resin, Blown Film specific Biaxial orientation in equipment.This film can be used for preparing tubulose heavy haul transport packaging bag.
In order to prepare the contractile film with high optical transparency, good retractable property and good mechanical properties, Britain Patent specification 2,097,324 is advised by stretching the film preparation film being made up of following homogenizing polymeric compositions:
(1) ethylene of 5-100wt% and at least one C8-C18The linear copolymer of-alpha-olefin, this polymer has 0.900-0.940g/cm3Density with by Differential Scanning Calorimetry (DSC) record less than the two of 128 DEG C different crystalline substances Body fusion zone, the temperature difference between two regions is at least 15 DEG C；With
(2) at least one of the copolymer selected from Alathon and ethylene and ethylenically unsaturated monomers of 0-95wt% is polymerized Thing, this polymer only has a crystal melting point under 128 DEG C.
The stretching of film must be carried out within the temperature range of two crystal melting points of copolymer (1) limit.Polymer (2) It is conventional ethylene homopolymer or copolymer.According to british patent specification 2,097,324, " conventional ethylene homopolymer or copolymer " It is the high density or Low Density Polyethylene prepared at high pressure or low pressure.According to british patent specification 2,097,324, this The conventional ethylene polymer only under 128 DEG C with a crystal melting point is not useable for preparing this shrink film, and ethylene is pungent with 1- (wherein alpha-olefin comonomer makes not observe second the linear copolymer of alkene or another alpha-olefin with considerably less amount existence DSC peak) it is also unsuitable for preparing this shrink film.This film is to prepare on the tubular membrane production line of the extrusion and orientation that combine film 's.British patent 2,097,324 teachings by with reference to U.S. Patent number 3,141,912, this tubular membrane by expansion and is longitudinally drawn Put in row orientation.By this film biaxial orientation the most in two mutually perpendicular directions do so.
U.S. Patent number 4,354,997,4,463,153 and 4,680,207, european patent application 0240705 and Europe are special Ethene polymers disclosed in profit description 866,820 and 2,097,324 and polymer composition can be used for preparing longitudinally and The film of double orientation while of transversely.But, it is only capable of the tubular membrane to blowing according to the teaching of file disclosed above and carries out double taking To.Specific processing line is needed for double orientation method.This processing line allows for maintaining permanent gas inside tubular membrane Pressure.The teaching of file disclosed above is not useable for the film of the i.e. non-ducted of double orientation casting films or other flat boards.
Flat Membrane (such as casting films) is typically to carry out double orientation at least two step, first in a direction, Then at other direction.Before attempting double orientation, on cast film line, by british patent specification 2, in 097,324 Flat Membrane prepared by disclosed polymer is unsuccessful, such as US5, as being reported in 589,561.
European patent application 0212731 is advised based on having less than 940kg/m3The Alathon of density or copolymer Preparation uniaxial orientation casting films.Ethene polymers can with high density polyethylene (HDPE) or polypropylene and/or different types of have low The Alathon or copolymer blended of density.Example uses and optionally mixes with other ethene polymerss less amount of Low density ethylene homo prepares uniaxial orientation film.
However, it has been viewed that due to the narrow orientation window of PE, polyethylene (PE) be oriented in flat board casting films stenter Bubbling method double with blowing are all extremely difficult.For double bubbling method, film converter is generally by PE and polypropylene (PP) Coextrusion or make PE crosslinking so that second time bubble stability.For tenter frame procedure, it is widely used in packaging industry With known PP as biaxial orientation PP(BOPP) film, and PE not yet passes the method and carries out industry system due to its narrow orientation window Make.
It is suitable that offer would is that based on polyvinyl new double orientation film, and this film can be by including that at least two is continuous Prepared by the method for orientation step, such as tenter frame procedure, and it is by using the processing conditions energy of the most such as temperature and draw ratio Enough select in relative broad range, and method parameter can change without causing this pair to take in drawing process to a certain extent To the physical loss of film quality.
Therefore, in one aspect, the present invention is for the method forming Biaxially oriented film, comprises the following steps: first select Selecting vistanex, wherein said vistanex includes linear low density polyethylene resin, described linear low density polyethylene Resin characteristics be have gross weight 9-35wt% the temperature more than 97.0 DEG C from crystallization Elution Fractionation (CEF) instrument elution The linear low density polyethylene resin gone out, and it is further characterized by comonomer distribution ratio (CDR) and the 0.15-with 33-80 The molecular weight ratio (Mw ratio) of 0.45.Then, the vistanex selected in the first step film is formed.Finally, this film is orientated, excellent Choosing is in the vertical with the range orientation of 3-5 times, in the horizontal with the range orientation of 3-7 times so that obtained film is characterized as tool Having: a) in the ultimate elongation that longitudinal direction (MD) is higher than laterally (CD), the ultimate elongation in longitudinal direction (MD) is laterally (CD) At least 1.5 times of ultimate elongation；B) at laterally 2% the highest secant modulus of ratio, it is in longitudinal direction at 2% horizontal secant modulus At least 1.25 times of 2% secant modulus；And c) have when the temperature exposure 10 minutes of 90 DEG C longitudinally less than 10% with at horizontal stroke To the free residual shrinkage rate less than 10%, more preferably in the free residual shrinkage rate all < 5% of vertical and horizontal.
On the other hand, the present invention is to include the film of vistanex, and this vistanex includes linear low density polyethylene Olefine resin, described linear low density polyethylene resin be characterized by the 9-35wt% of gross weight in the temperature more than 97.0 DEG C At the linear low density polyethylene resin that CEF elutes out, and it is further characterized by the Mw with CDR and 0.15-0.45 of 33-80 Ratio, wherein this film is characterized by: a) in the longitudinally the highest ultimate elongation of ratio, be laterally in longitudinal ultimate elongation At least 1.5 times of ultimate elongation；B) at laterally 2% the highest secant modulus of ratio, it is vertical at 2% horizontal secant modulus To at least 1.25 times of 2% secant modulus；And c) have when the temperature exposure 10 minutes of 90 DEG C longitudinally less than 10% and The laterally free residual shrinkage rate less than 10%, more preferably in the free residual shrinkage rate all < 5% of vertical and horizontal.
Accompanying drawing is sketched
Fig. 1 is the ultimate seal strength the showing embodiment 1-2 chart as the function of seal temperature.
Fig. 2 is the heat-blocking (hot tack) the showing embodiment 1-2 chart as the function of seal temperature.
Detailed description of the invention
Method of testing
Unless otherwise noted, throughout the specification, following character is to be measured by shown method of testing.
Density measures according to ASTM D-792.
The melt index of ethene polymers (i.e. including those polymer of the unit being derived from vinyl monomer of at least 50wt%) Or I2It is to measure according to ASTM D1238,190 DEG C, 2.16kg.
Hot strength, ultimate elongation and 2% secant modulus are to be measured by ASTM D882 with ZWICK universal tester 's.
Dart impact Ceast dart impact tester is tested by ASTM D1709.
Heat-blocking be on J&B heat-blocking tester 400 with the sample of 25mm width, the Sealing period of 0.5 second and 0.275N/mm2Seal pressure carry out.The back side of sealed sample it is attached to polyethylene terephthalate (PET) adhesive tape. Peeling speed is 200mm/sec.Time delay is 0.1 second.
Testing for sealing intensity, heat seal is carried out on J&B heat-blocking tester 400.Sample Width, sealing Parameter is identical in all testing with heat-blocking with back of the body patch.Sealing intensity is the peeling speed after regulating 24 hours with 500mm/s Degree is test on ZWICK universal tester.
Free residual shrinkage rate is by following mensuration:
Shrinkage factor %=(L1-L2)/L1×100
Wherein L1Sample length before the heat treatment, L2It it is the sample in the stove balanced with specified temp after 10 minutes Product length.Use two kinds of different furnace temperature (70 DEG C and 90 DEG C).Before heat treatment, sample size is 6cm x 6cm(L1=6cm).
Surface tension can measure according to ASTM D2578-09.
CEF method
Crystallization Elution Fractionation (CEF) is by Monrabal etc.,Macromol.Symp.257,71-79 (2007) describe. This apparatus preparation has IR-4 detector (such as PolymerChar, Spain commercially sell) and double angle scattering measuring Device Model2040(such as Precision Detectors commercially sells).This IR-4 detector is in a joint manner with two Individual light filter C006 and B057 operates.By the 50X4.6mm guard columns of 10 microns, (such as Polymer Labs commercially sells ) be arranged in detector stove before IR-4 detector.Obtain o-dichlorobenzene (ODCB, 99% anhydrous grade) and 2,5-bis-- Tertiary butyl-4-methylphenol (BHT) (the most commercially available from Sigma-Aldrich's).Also obtain silica gel 40(particle diameter 0.2～0.5mm) (the most commercially available from EMD Chemicals's).This silica gel is existed the most in a vacuum furnace 160 DEG C are dried about 2 hours.800 milligrams of BHT and 5 grams of silica gel are added in 2 liters of ODCB.The ODCB comprising BHT and silica gel is present It is referred to as " ODCB ".Before use by ODBC with dry nitrogen (N2) spray 1 hour.Dry nitrogen be by by nitrogen so that < 90psig leads to Cross CaCO3WithObtain on molecular sieve.Rock 2 hours at 160 DEG C with Autosampler and carry out sample system with 4mg/ml Standby.Volume injected is 300 μ l.The temperature curve of CEF is: with 3 DEG C/min from 110 DEG C to 30 DEG C of crystallizations, 30 DEG C of thermal balances 5 points Clock (including the solvable fraction elution time being set as 2 minutes) and with 3 DEG C/min from 30 DEG C to 140 DEG C of elutions.At crystallization process In flow velocity be 0.052ml/min.Flow velocity in elution process is 0.50ml/min.These data are with a data point per second Collect.
CEF post is filled with the bead of 125 μm ± 6% (the most commercially available from MO-SCI Specialty Those of Products), according to US2011/0015346A1, there is 1/8 inch of rustless steel sleeve pipe.The internal liquid volume of CEF post For 2.1-2.3mL.By use NIST standard reference material polyethylene 1475a(1.0mg/ml) and icosane (2mg/ml) exist Mixture in ODCB carries out temperature correction.This correction is made up of four steps: (1) computing relay volume, and it is defined as recording The highest elution temperature of icosane deduct the temperature compensation value (temperature offset) between 30.00 DEG C；(2) will CEF raw temperature data deducts the temperature compensation value of this elution temperature.Notice that this temperature compensation value is that experiment condition such as elutes The function of temperature, elution flow velocity etc.；(3) linearity correction line is set up, this elution of scope up conversion of 30.00 DEG C and 140.00 DEG C Temperature makes the peak temperature that NIST linear polyethylene 1475a has 101.00 DEG C, and icosane has the peak value temperature of 30.00 DEG C Degree；(4) the solvable fraction measured for 30 DEG C of isothermals, by using the elution rate of heat addition of 3 DEG C/min by this elution temperature line Property extrapolation.Obtaining reported elution peak temperature makes the co-monomer content calibration trace observed meet US2011/ Those reported before in 0015346A1.
CDR method
At T1(DEG C) and T2(DEG C) between elution temperature range in the percentage by weight of material of elution be defined as at T1- Total long-pending divided by 25.5-118.0 DEG C of the integration of IR-4 chromatogram (deducting the TCH test channel of baseline) in the elution temperature range of T2 Point, as shown in equation 1 to equation 5, wherein T is elution temperature (correction from above-mentioned).Comonomer distribution ratio (CDR) as Calculate shown in equation 6:
Comonomer distribution ratio (CDR)=log9(equation 2) (equation 3) (equation 4)) * (equation 5) equation 6 is by selecting Two data point calculation linear baseline: one polymer elute before, generally the temperature of 26 DEG C；Another is washed at polymer After carrying, generally at 118 DEG C.For each data point, before integration, detector signal is deducted baseline.
Mw ratio
Polymer molecular weight can be directly near according to Rayleigh-Gans-Debys by light scattering (LS) and concentration detector Like method (A.M.Striegel and W.W.Yau, Modern Size-Exclusion Liquid Chromatography, 2nd Edition, Page242and Page263,2009) by assuming that shape factor is 1 and assumes that all virial coefficients are 0 to carry out Measure.By LS(90 degree) and IR-4(TCH test channel) chromatogram deducts baseline.For whole resin, set integration window and include All chromatograms in the elution temperature range (temperature correction is described above) of 25.5-118.0 DEG C.Molecular weight ratio (Mw ratio) includes Following steps:
(1) offset between detector is measured.Offset be defined as LS with IR-4 detector compared with geometric volume compensate Value.It is calculated as the difference of elution volume (mL) at polymer peak between IR-4 and LS chromatogram.By use elute hot speed and Elution flow velocity is translated into temperature compensation value.High density polyethylene (HDPE) is used (not have comonomer, I2Being 1.0, conventional GPC oozes The polydispersity of saturating chromatography determination or molecular weight distribution Mw/MnIt is about 2.6).Outside divided by lower parameter, use and CEF method above Identical experiment condition: with 10 DEG C/min from 140 DEG C to 137 DEG C of crystallizations, wash as solvable fraction for 1 minute at 137 DEG C of thermal balances Carry the time, with 1 DEG C/min from 137 DEG C-142 DEG C elutions.Flow velocity in crystallization process is 0.10ml/min.Stream in elution process Speed is 0.80ml/min.Sample concentration is 1.0mg/ml.
(2) before integration, each data point in LS chromatogram is moved to correct the offset between detector.
(3) LS and the IR-4 chromatogram of baseline will be deducted in the elution temperature range of 25.5-118.0 DEG C and 97.0- Integration in the elution temperature range of 118.0 DEG C.
(4) molecular weight ratio (Mw than) is calculated according to equation 7:
By the white noise level of LS chromatogram calculation LS detector (90 degree) before polymer elutes.First to LS chromatograph Figure carries out Baseline wander to obtain deducting the signal of baseline.By at least 100 data point meters before using polymer to elute Calculate the LS white noise standard deviation as the LS signal deducting baseline.In measuring for offset between detector, use does not has altogether Poly-monomer, I2 are 1.0, polydispersity Mw/MnBeing about the high density polyethylene (HDPE) of 2.6, the typical white noise of LS is 0.20-0.35mV, Whole polymer has the peak height deducting baseline that ordinarily be about 170mV.Should keep noting high density polyethylene (HDPE) is provided extremely Signal/the noise ratio of few 450 ratio of white noise (peak height of total polymer with).
Differential Scanning Calorimetry (DSC) is used to measure fusing point.Polymer samples is pressed into thin film the temperature of 350 °F (suppressing 10 minutes with 1,500psi).Weigh about 5-8mg sample and put in DSC dish.Lid is clamped on dish, guarantees envelope Hold one's breath atmosphere.Specimen disc is placed on DSC(TA Instruments DSC Q1000) in unit, then adding with about 100 DEG C/min Hot speed is heated to the temperature than high at least 30 DEG C of melting point polymer or 180 DEG C.This sample is kept about 5 minutes in this temperature. Then this sample is cooled to the temperature than low at least 50 DEG C of crystallization temperature or-40 DEG C with the speed of 10 DEG C/min, and in this temperature Degree isothermal keeps 5 minutes.Then sample is heated until completing fusing with the speed of 10 DEG C/min.Record cooling and second time add Heating curve.By starting to-20 DEG C to set baseline end point analysis cooling curve from crystallization.By setting to fusing end from-20 DEG C Determine baseline end point analysis heating curves.The value measured is peak melting point (Tm), high crystallization temperature (Tc), heat of fusion (Hf) (unit For J/g), use equation 8 to calculate degree of crystallinity % of polyethylene specimen:
Degree of crystallinity %=((Hf)/(292J/g)) × 100 equations 8
Heat of fusion (H is reported from second time heating curvesf) and peak melting point.High crystallization temperature is to be recorded by cooling curve 's.
The baseline correction of TA Instruments DSC Q1000 is carried out by the following correction guide in software.First, Obtain baseline by this unit is heated to 280 DEG C from-80 DEG C, in DSC aluminum dish, there is no any sample.Then, according to this to Instruction in leading uses sapphire standard.Then by sample being heated to 180 DEG C, by sample with the cooldown rate of 10 DEG C/min Be cooled to 120 DEG C, then keep sample isothermals 1 minute at 120 DEG C, then by this sample with the rate of heat addition of 10 DEG C/min from 120 DEG C are heated to 180 DEG C, analyze the fresh indium sample of about 1-2mg.The heat of fusion and the fusing that measure indium sample start temperature, and Verification fusing beginning temperature is in the range of 0.5 DEG C of 156.6 DEG C, and verification heat of fusion is in the range of the 0.5J/g of 28.71J/g.So Afterwards by the droplet of the fresh sample in DSC dish is cooled to-30 DEG C of analyses with the cooldown rate of 10 DEG C/min from 25 DEG C Ionized water.Sample is kept 2 minutes at-30 DEG C of isothermals, with the heating rate to 30 DEG C of 10 DEG C/min.Mensuration fusing starts Temperature, checks it in the range of 0.5 DEG C of 0 DEG C.
CEF and DSC is tested, uses the blend of two kinds of resins in some cases.This blend is by with institute The component 50g bowl needing percentage by weight to add total 50 grams is prepared on Haake Rheomix.Three temperature of Haake District sends out and is set as 175 DEG C.By sample with 50RPM(revolutions per minute) hash total 10 minutes, wherein use and within 5 minutes, reach maximum Moment of torsion, uses 5 minutes biased samples.
One aspect of the present invention is for the method forming Biaxially oriented film, comprises the following steps: a) select polyolefin Resin, wherein said vistanex include being characterized by the 9-35wt% of gross weight in the temperature more than 97.0 DEG C from CEF The line of the Mw ratio of the linear low density polyethylene resin eluted out and CDR and 0.15-0.45 being further characterized by having 33-80 Property ldpe resin；B) film is formed by the vistanex selected in step (a)；And c) by formation in step (b) Film is orientated, preferably the scope at longitudinal 3-5 times and the scope at horizontal 4-7 times, and wherein this film is characterized by: a) at longitudinal ratio The highest ultimate elongation, is at least 1.5 times of horizontal ultimate elongation in longitudinal ultimate elongation；B) laterally Than 2% longitudinally the highest secant modulus, it is at least 1.25 times of 2% longitudinal secant modulus at 2% horizontal secant modulus；And c) Have longitudinally less than 10% with in laterally free residual shrinkage rate less than 10% when the temperature exposure 10 minutes of 90 DEG C, more excellent It is selected in vertical and horizontal and is both less than 5%.Preferably this film has when the temperature exposure 10 minutes of 70 DEG C longitudinally less than 5% with at horizontal stroke To the free residual shrinkage rate less than 5%.
The vistanex used in the present invention includes linear low density polyethylene (LLDPE) resin.LLDPE includes neat lattice Strangle-Natta-catalyzed linear low density polyethylene, (including metallocene) linear low density polyethylene (m-of single site catalysed LLDPE) and medium density polyethylene (MDPE), as long as this MDPE has not higher than 0.940g/cm3Density；And it is aforementioned The combination of two or more.These polyvinyl resins are as known in the art.The LLDPE resin being best suited in the application Three below parameter characterization can be used.
First parameter of LLDPE used in the present invention be have gross weight 9-35wt% in the temperature more than 97 DEG C The linear low density polyethylene resin that degree elutes out from CEF.Preferably more than 25% is to elute out in the temperature more than 97 DEG C.
The second parameter of LLDPE used in the present invention is the CDR with 33-80.
3rd parameter of LLDPE used in the present invention is to have the Mw ratio of 0.15-0.45.Preferably this Mw ratio is less than 0.35。
LLDPE preferably has greater than or is equal to the peak melting point of 120 DEG C.
LLDPE preferably has at 1-30g/10 minute, melt index in the range of preferably 2-15g/10 minute (190 DEG C, 2.16kg).
LLDPE preferably has at 0.90-0.94g/cm3, preferably 0.91-0.935g/cm3In the range of density.
Preferably, polyvinyl resin used in the present invention is single resin, although above-mentioned material (includes with other resins The polyolefin tree of the alpha-olefin (being i.e. derived from the alkene with the monomer more than 2 carbon) of other polyvinyl resins and higher level Fat) blend and copolymer can also use.In preferred embodiments, this film will only include polyvinyl resin, but poly-third Alkene also be able to be blended or coextrusion in this membrane structure.In some embodiments, this vistanex preferably includes to be less than The polypropylene of 1wt%.
Vistanex used in the present invention can comprise one or more additives well known in the art.This interpolation Agent includes antioxidant (such as IRGANOX1010 and IRGAFOS168(Ciba Specialty Chemicals; Glattbrugg, Switzerland)), UV absorbers, antistatic additive, pigment, dyestuff, nucleator, filler, slipping agent, Fire retardant, plasticizer, processing aid, lubricant, stabilizer, smoke suppressant, viscosity-control additive, surface modifier and antiblocking agent. Weight based on this polyolefin polymer, this polyolefine resin composition can the most such as include the one less than 10% or The gross weight of multiple additives.
Second step in the method for first embodiment of the invention is that the vistanex selected by the first step forms film Breadth.Film can be prepared according to any means as known in the art.Casting films is method commonly used in the art.
Once define film, just pass it through tenter frame procedure, wherein first film is orientated in longitudinal direction (MD), then In laterally (CD) orientation.It is 3-5 times at longitudinal orientation ratio, is laterally being 3-7 times.Orientation can be carried by this tenter frame procedure Supply.
Another aspect of the present invention is the Biaxially oriented film including vistanex, and wherein this vistanex includes linearly Ldpe resin, described linear low density polyethylene resin is characterized by being more than of the 9-35wt% of gross weight Linear low density polyethylene resin that the temperature of 97.0 DEG C elutes out from CEF and the CDR being further characterized by there is 33-80 and The Mw ratio of 0.15-0.45, wherein this film is characterized as when the temperature exposure 10 minutes of 90 DEG C having longitudinally less than 10% with at horizontal stroke To the free residual shrinkage rate less than 10%, more preferably both less than or it is equal to 5% at vertical and horizontal.Prepared by the method for the present invention Film be further characterized by having longitudinally than the percentage elongation of the highest at least 1.5 times (more preferably at least 1.75 or even 2 times). Further, this film can be characterized by horizontal 2% secant modulus than longitudinally high at least 1.25 times, the fewest 1.5 or even 1.75 times.
On the other hand, the film of the present invention surface treated can reach more than the surface tension of 38 dyne/cm, the most such as By sided corona treatment or flame treatment as known in this field.Surface processes and contributes to making printing and the laminating method energy in downstream Enough feasible.
The film of the present invention can be monofilm or multilayer film, and wherein integral membrane structure meets the qualifications of claim. For multilayer film, preferably this film includes one or more sandwich layer and two cortexes, and at least one of which sandwich layer has ratio at least The higher density of individual cortex.
On the other hand, the film of the present invention can close structure with other matrix lamination cambium layer.Be suitable for matrix include but It is not limited to biaxially oriented polypropylene film, orientation PET film, oriented polyamide film, is blow molded and is cast PE film, aluminium foil and paper.
Experiment
In order to verify effectiveness of the invention, it is prepared for a series of alignment films.This film uses the following resin in table 1.CEF Result is summarized in table 2, and DSC result is summarized in table 3.For DSC result, it is shown that all fusing point (Tm1-Tm3) and all knots Brilliant point (Tc1-Tc3) result.For CEF and DSC data, it is shown that the sandwich layer (25%A/75% of the film embodiment 2 shown in table 4 B) result of the percent of total (53%A/47%B) of resin used in blend in and the film embodiment 2 of table 4.
Table 3:DSC result
On special stenter double orientation production line, trilamellar membrane is prepared according to table 4.
Table 4: the trilamellar membrane of preparation on stenter double orientation production line
Embodiment # Layer A Layer B Layer C
1 A A A
2 A 25%A/75%B A
3 (contrasts) C C C
4 (contrasts) E E E
5 (contrasts) D D D
This stenter production line have three-layer co-extruded go out production line.The output of three extruders is than for 1:5:2.From flat-die After mouth extrusion, this film is cooled down on chill roll, and is immersed in the water-bath being filled with room temperature water.Then by this curtain coating Film has the roller of different rotation rates to realize longitudinal stretching by a series of.Longitudinal stretching part at this manufacturing line In have three pair roller barrels, its all with oil heating.First pair roller barrel preheats.Second pair is stretching roller.Last pair roller barrel For relaxing and annealing.The temperature of each pair roller barrel controls respectively.After longitudinal stretching, this film web face is added by comprising 7 The stenter hot-air furnace of hot-zone is to implement cross directional stretch.First three district is used for preheating, and Liang Ge district subsequently is used for stretching.? Last two zones is used for annealing.The temperature in each district controls respectively.Each roller for longitudinal stretching and each roller for cross directional stretch All temperature of cylinder are listed in " longitudinal drawing temperature " and " transverse drawing temperature " hurdle of table 5.This special stenter production line Horizontal orientation ratio is fixed on 5.5 times.Longitudinal stretching ratio is maintained at 4 times.Table 5 lists detailed method information.
Table 5: the method detailed information of the film of preparation on stenter production line
The processing result of these films is as follows: for embodiment 1, film preparation was steadily being carried out more than 1 hour, in preparation process In there is no film rupture.For embodiment 2, film preparation was steadily carried out at 40 minutes, did not had film rupture in preparation process.For reality Execute the contrast of example 3(), during cross directional stretch, this film web face ruptures for every 1-2 minute.Embodiment 4(is contrasted), at horizontal stroke In drawing process, this film web face ruptures for every 2-3 minute.Embodiment 5(is contrasted), this film during cross directional stretch Breadth always ruptures, and does not collects continuous print film.Table 6 shows the average thickness of collected film and the standard deviation of thickness Difference.
Table 6: the average thickness of collected film and standard deviation thereof
In order to observe film processing and film thickness change, it is possible to infer that the film embodiment 1 of the present invention and embodiment 2 can be Commercial enforcement, but comparative example 3-5 can not commercially be prepared, because film rupture frequently and bigger thickness can occur Degree change.It is an object of the present invention to prepare and there is acceptable physical property (such as residual shrinkage rate, sealing intensity and heat Seal and start temperature) and there is the film of acceptable machining feature (such as this film can commercially be prepared) simultaneously.
Applying for most of flexible packagings, residual shrinkage rate is not required character.This is because high residual shrinkage rate (winkles) or dimensional instability is tilted by causing sealing in the lamination or printing process in downstream.Although can pass through Annealing conditions is fine-tuned in commercialization preparation and reduces residual shrinkage rate further, but the film of embodiment 2 shows residual shrinkage rate Minimum, embodiment 1 confirms that commercially acceptable residual shrinkage rate is less than 10%.It should be noted that while comparative example 3 and 4 tool There is the residual shrinkage rate lower than inventive embodiments 1, but these films are owing to occurring frequently in method for alignment as above Film rupture and commercially would is that unacceptable.Residual shrinkage rate result shows in table 7.
Table 7: collected film is residual shrinkage rate % of 70 DEG C and 90 DEG C
Then the film of the present invention is evaluated to measure the limit heat sealing intensity when various seal temperature and Hot tack strength, As shown in Fig. 1 and 2 and Biao 8 and 9.The data of comparative film are not shown, because it can not be implemented under commercial terms.
Table 8: the Seal strength data of collected film
Table 9: the Seal strength data of collected film
Embodiment 1 and the tensile property of embodiment 2 and dart impact resistance data are listed in Table 10.Further comprises 100% tree The representative property of 20 and 25 microns of casting films that fat A and 100% resin B are made, to compare orientation after-drawing intensity, modulus and to resist The raising of impact.Two kinds of monolayer cast film of Resin A and resin B all prolong at five laminar flows to be prepared on production line, uses phase Same fusion temperature (273-274 DEG C) and chill-roll temperature (21 DEG C), but use the different line speed (films to Resin A For 122m/min；Film to resin B is 183m/min).The physical property of the film of the present invention is significantly improved by orientation.
Table 10: embodiment 1 and embodiment 2 and 100% Resin A prepared by casting films method and the stretching of 100% resin B Character and dart impact character
* estimated value
The film of table 10 is prepared on pilot production line, its surface processing device not added.But under being used for For the commercialization preparation of trip printing or lamination, preferably carry out surface process (such as sided corona treatment).The film of the present invention can layer Close on matrix (such as PET, double orientation polyamide (BOPA) and/or Bioriented polypropylene (BOPP) film) to be formed for softness The laminate structures of packaging.
Embodiments below is deemed within the scope of the present invention, applicant retain modification right require or propose one or More than one piece adds applies for being distinctly claimed these embodiments any of the most clearly addressing at present listed claim Right.And, it is expressly contemplated that the restriction of middle proposition set forth below can combine with the most inconsistent any order.
1. the method forming Biaxially oriented film, comprises the following steps:
A. select vistanex, wherein said vistanex to include linear low density polyethylene resin, described linearly Ldpe resin is characterized by the line eluted out in the temperature more than 97.0 DEG C of the 9-35wt% of gross weight from CEF Property ldpe resin, and it is further characterized by the Mw ratio with CDR and 0.15-0.45 of 33-80；
B. film is formed by the vistanex selected in step (a)；
C. the film formed in step (b) is orientated；
Wherein this film is characterized by the longitudinally the highest ultimate elongation of ratio, is at horizontal stroke in longitudinal ultimate elongation To at least 1.5 times of ultimate elongation, with at 2% laterally higher than longitudinal direction secant modulus, 2% horizontal secant modulus be At least 1.25 times of 2% longitudinal secant modulus；
With
Wherein this film is characterized as when the temperature exposure 10 minutes of 90 DEG C having longitudinally less than 10% and being laterally less than The free residual shrinkage rate of 10%.
2. the method for embodiment 1, the film wherein formed in step (b) is longitudinally with the range orientation of 3-5 times and at horizontal stroke To with the range orientation of 3-7 times.
3. the method for embodiment 1, wherein this film is characterized by longitudinal percentage elongation is at horizontal percentage elongation At least 1.75 times.
4. the method for embodiment 1, wherein this film is characterized by longitudinal percentage elongation is at horizontal percentage elongation At least 2 times.
5. the method for embodiment 1, wherein this film is characterized by 2% longitudinal secant modulus horizontal 2% is just Cut modulus at least 1.5 times.
6. the method for embodiment 1, wherein this film is characterized by 2% longitudinal secant modulus horizontal 2% is just Cut modulus at least 1.75 times.
7. the method for embodiment 1, wherein the free residual shrinkage rate of 90 DEG C at least one vertical or horizontal side To less than 5%.
8. the method for embodiment 1, wherein this vistanex has the peak melting point more than or equal to 120 DEG C.
9. the method for embodiment 1, wherein this vistanex has the melt index in the range of 1-30g/10 minute (190 DEG C, 2.16kg).
10. the method for embodiment 1, wherein this vistanex has the melt index in the range of 2-15g/10 minute (190 DEG C, 2.16kg).
The method of 11. embodiments 1, wherein this vistanex has at 0.90-0.94g/cm3In the range of density.
The method of 12. embodiments 1, wherein this vistanex has at 0.91-0.935g/cm3In the range of density.
The method of 13. embodiments 1, wherein this vistanex includes the polypropylene less than 1wt%.
The method of 14. embodiments 1, wherein this vistanex is substantially by linear low density polyethylene with selected from smooth One or more additives composition of agent, antiblocking agent, polymer processing aids or coloring pigment.
The method of 15. embodiments 1, wherein uses stenter to be orientated this film.
The method of 16. embodiments 1, wherein this vistanex not yet cross-links.
The method of 17. embodiments 1, had wherein longitudinally been orientated this film before horizontal orientation.
18. Biaxially oriented films, including:
Vistanex, wherein said vistanex includes linear low density polyethylene resin, described linea low density Polyvinyl resin be characterized by the 9-35wt% of gross weight the temperature more than 97.0 DEG C from CEF elute out linear low close Degree polyvinyl resin, and it is further characterized by the Mw ratio with CDR and 0.15-0.45 of 33-80；
Wherein this film surface treated is to present more than or equal to the capillary surface tension of 38 dyne/cm；Wherein should Film is characterized by the longitudinally the highest ultimate elongation of ratio, is in horizontal ultimate elongation in longitudinal ultimate elongation At least 1.5 times, and laterally than 2% the highest secant modulus, be the 2% secant mould in longitudinal direction at 2% horizontal secant modulus At least 1.25 times of amount；
Wherein this film is characterized as when the temperature exposure 10 minutes of 90 DEG C having longitudinally less than 10% and being laterally less than The free residual shrinkage rate of 10%.
The film of 19. embodiment 18 preparations, wherein this film has the thickness of 10-100 micron.
The film of 20. embodiments 19, wherein this film has the thickness of 20-50 micron.
The film of 21. embodiments 18, wherein this film is monofilm.
The film of 22. embodiments 18, wherein this film is multilayer film.
The film of 23. embodiments 22, wherein this film includes one or more sandwich layer and two cortexes, and wherein this at least one Individual sandwich layer has the density higher than at least one cortex.
24. 1 kinds of laminate film structures, it includes matrix, and wherein the film of embodiment 18 is laminated on matrix.
The laminate film structure of 25. embodiments 24, wherein one or more in following of this matrix: double orientation poly-third Alkene film, orientation polyethylene terephthalate film, oriented polyamide film, be blow molded or be cast PE film, aluminium foil and paper.
The method of 26. embodiments 1.Wherein this polyethylene film has the heat of fusion more than 137J/g.
Although the present invention having been had been described in considerable detail by description above and embodiment, but this details being for example Purpose and be not construed as the restriction to the scope of the present invention described in appended claim.Allow in laws and regulations In the case of, the patent application of all United States Patent (USP)s identified above, disclosed patent application and mandate is all passed through with reference to drawing Enter herein.

Claims (19)

1. the method forming Biaxially oriented film, comprises the following steps:
A. vistanex, wherein said vistanex is selected to include linear low density polyethylene resin, described linear low close Degree polyvinyl resin is characterized by washing in the temperature more than 97.0 DEG C of the 9-35wt% of gross weight from crystallization Elution Fractionation The linear low density polyethylene resin proposed, and it is further characterized by comonomer distribution ratio and the 0.15-with 33-80 The Mw ratio of 0.45, the melt index of described linear low density polyethylene resin is 1-30g/10min, according to ASTM D1238,190 DEG C, 2.16kg measures；
B. film is formed by the vistanex selected in step a)；
C. being orientated by the film formed in step b), the film wherein formed in step b) is longitudinally with the range orientation of 3-5 times And laterally with the range orientation of 3-7 times；
Wherein this film is characterized by the longitudinally the highest ultimate elongation of ratio, is horizontal in longitudinal ultimate elongation At least 1.5 times of ultimate elongation, and at laterally 2% the highest secant modulus of ratio, be vertical at 2% horizontal secant modulus To at least 1.25 times of 2% secant modulus；With
Wherein this film is characterized as when the temperature exposure 10 minutes of 90 DEG C having longitudinally less than 10% with laterally less than 10% Free residual shrinkage rate.
2. the process of claim 1 wherein that this film is characterized by longitudinal percentage elongation is at least the 2 of horizontal percentage elongation Times.
3. the process of claim 1 wherein that this film is characterized by 2% longitudinal secant modulus is in 2% horizontal secant At least 1.75 times of modulus.
4. the process of claim 1 wherein that this free residual shrinkage rate at least one vertical or horizontal direction is less than 5%.
5. the process of claim 1 wherein that this vistanex has the peak melting point more than or equal to 120 DEG C and is more than The heat of fusion of 137J/g.
6. the process of claim 1 wherein that this vistanex has the melt index of 2-15g/10 minute, according to ASTM D1238,190 DEG C, 2.16kg measures.
7. the process of claim 1 wherein that this vistanex has 0.91-0.935g/cm3Density.
8. the process of claim 1 wherein that this vistanex includes the polypropylene less than 1wt%.
9. the process of claim 1 wherein that this vistanex is substantially by linear low density polyethylene with selected from slipping agent, anti- One or more additives composition of adhesion agent, polymer processing aids or coloring pigment.
10. the process of claim 1 wherein that this film is orientated by use stenter.
11. the process of claim 1 wherein that this vistanex not yet cross-links.
12. the process of claim 1 wherein the orientation carried out before horizontal orientation by this film in the vertical.
13. Biaxially oriented films, including:
Vistanex, wherein said vistanex includes linear low density polyethylene resin, described linear low density polyethylene Olefine resin be characterized by the 9-35wt% of gross weight the temperature more than 97 DEG C from crystallization Elution Fractionation elute out linear Ldpe resin, and it is further characterized by the comonomer distribution with 33-80 than the Mw ratio with 0.15-0.45, institute The melt index stating linear low density polyethylene resin is 1-30g/10min, and according to ASTM D1238,190 DEG C, 2.16kg surveys Fixed；
Wherein this film surface treated is to present more than or equal to the capillary surface tension of 38 dyne/cm；Wherein this film is special Levy as having in the longitudinally the highest ultimate elongation of ratio, be in horizontal ultimate elongation extremely in longitudinal ultimate elongation Few 1.5 times, and at laterally 2% the highest secant modulus of ratio, be at 2% longitudinal secant mould at 2% horizontal secant modulus At least 1.25 times of amount, wherein said film is longitudinally with the range orientation of 3-5 times and at the horizontal range orientation with 3-7 times；
Wherein this film is characterized as when the temperature exposure 10 minutes of 90 DEG C having longitudinally less than 10% and being laterally less than The free residual shrinkage rate of 10%.
The film of 14. claim 13, wherein this film has the thickness of 20-50 micron.
The film of 15. claim 13, wherein this film is monofilm.
The film of 16. claim 13, wherein this film is multilayer film.
The film of 17. claim 16, wherein this film includes one or more sandwich layer and two cortexes, and at least one of which sandwich layer There is the density higher than at least one cortex.
18. 1 kinds of laminate film structures, it includes matrix, and wherein the film of claim 17 is laminated on this matrix.
The laminate film structure of 19. claim 18, wherein one or more in following of this matrix: Bioriented polypropylene Film, orientation polyethylene terephthalate film, oriented polyamide film, be blow molded or be cast PE film, aluminium foil and paper.
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